W-Propyl iodide

Synonym monoiodopropane, w-propyl iodide, propyl iodide... 

We may use the observations listed above to derive in some cases the temperature coefficients of the rate of pyrolysis and hence the activation energy of the reaction. For w-propyl iodide and n-butyl iodide we have sufficiently reliable data for two temperatures from which we calculate for -propyl 0 = 52 kcal. and for -butyl Q = 53 kcal. This lends support to the value of similar magnitude, Q — 55 kcal., obtained from the otherwise less reliable Exps. 3, 4, and 6, 7, 8 for ethyl iodide. 

Dimethylindole magnesium iodide reacts with chloroacetonitrile in ether to give 3-cyanomethyl-2,3-dimethylindolenine (234). Majima and Hoshino obtained 3-(2-cyanoethyl)lndole (235) by the action of -chloropropionitrile on indole magnesium iodide. The reaction was slower with -chloropropionitrilc than with chloro-aoetonitrile. 3-(3-Cyano-w-propyl)indole (236), required as an intermediate in the synthesis of 3-indolyl-y-w-butyric acid, was prepared, but not isolated, by the action of y-chloro-w-butyronitrile on indole magnesium iodide. ... 

Zinc Dipropyl. Zn(C3H7)2, C6H14Zn mw 151.5 5 mobile pyrophoric liq, stable in a sealed tube under C02 bp 160° d 1.1034g/cc at 20/4° RI 1.4845 at 18.6°. Sol in org solvents decomps explosively on contact with w. Prepn is by reacting n-propyl iodide with Zn. The compd has a heat of combstn of 11133 5.6 kcal/mole(Refs3,p 181 6, p 491M-444)... 

Other iV-alkyl-w-toluidines may be prepared by practically the same procedure. The submitters report that w-propyl, iso-propyl, and -butyl derivatives are obtained readily from m-toluiriine and the appropriate alkyl iodides (rather than the bromides). In these cases the alkylation is effected by placing the sealed bottle in a beaker of water which is warmed gradually to 70-80° and kept in a warm place until the reaction is completed usually several days are required. 

The formation of w-propyl and -butyl iodides is a side reaction in the preparation of cyclopropane derivatives from olefins by the reaction with diethylzinc and em-diiodoalkanes 163). This side reaction is enhanced by the presence of lithium or magnesium halides, and was explained in terms of insertion of the zinc carbenoid into the carbon-iodine bond 245). 

The ethyl, w-propyl, n-butyl and allyl iodides were commercial products, carefully purified before use, while the other iodides were prepared and purified by standard methods. Cylinder nitrogen was freed from oxygen by passage over sodium at 350°, and cylinder hydrogen was purified by passage through a palladium thimble. Pure nitric oxide was made by the method of Giauque and Johnston. 

We take this to be the explanation for the observed fall of D from methyl to ethyl iodide, and we would extend the scheme to include the further fall of D observed for w-propyl and -butyl iodide, as follows ... 

Aza-3,4-benzo-5,6-dipropylpentatriafulvalene hydriodide (373) was obtained in 20% yield by the action of 1,2-di-w-propyl-3 -ethoxy-cyclopropenium fluoroborate on indole magnesium iodide in a methylene chloride-ether mixture.167... 

With minor modifications, this method is suitable for the preparation of ethyl, w-propyl, n- and iso-butyl and n- and iso-amyl iodides with yields above 90 per cent. A somewhat lower yield is obtained in the preparation of sec.-butyl iodide owing to the formation of hydrogen iodide. 

Tetrapropylstibonium iodide, (C3H7)4SbI, occurs as its double salt with mercuric iodide, CiaHgsSbl.Hgla, when antimony amalgam, SbgHgg, is heated wnth propyl iodide in a sealed tube at 183° C. It may also be obtained by the interaction of propyl iodide and a potassium-antimony alloy. The mercuri-iodide mentioned above forms yellow, crystalline columns, M.pt. 103-5° C., readily soluble m acetone, insoluble in w ater or ether. 

Methyl and 6-methyl-6-w-propyl substituted 2,4-dimethoxy-pyrimidines react with methyl iodide, as does the simple dimethoxy compound, to give methoxypyrimidones, but the 6-chloro-2,4-dimethoxy derivative (47) is affected only at 100°, when it gives 4-chloro-1,3-dimethyluracfl (48). ... 

The reactivity is further influenced by the branching of the carbon chain and by the possible presence of a double bond and position of a second halogen atom. Among the tested monovalent and divalent halo compounds (5), methyl iodide, allyl bromide, benzyl bromide, and methylene iodide were found most reactive, a medium reactivity was observed for penta-methylene bromide, ethyl bromide, w-propyl bromide, n-butyl bromide, and w-amyl bromide, while ethylene bromide and isobutyl bromide reacted most slowly. 

At low temperatures perfluoro-w-propyllithium, prepared in the above manner, underwent displacement and addition reactions common to alkyl-lithium compounds. The experimental technique (7) involved addii methyllithium and the reactant dissolved in ether to heptafluoro- -propyl iodide in the same solvent. In this manner, certain aldehydes and ketones afforded the expected alcohols, and diethyldichlorosilane gave a mixture of the organosilanes n-C3F7(C2H5)2SiCl and ( -C3F7)2Si(C2H5)2. 

Recently the direct synthesis and the stability of perfluoro-w-propyl-lithium has been the subject of a careful study (8). Although heptafluoro-propyl iodide does not react with lithium metal in pentane or diethyl ether at temperatures between —50° and 20° C, a vigorous reaction occurs at —74° C between the iodide and lithium containing 2% sodium when diethyl ether is the solvent. Among the reaction products are hexafluoropropene, fluorine-containii pol)rmers, andatraceof heptafluoropropane. Formation of heptafluoropropane can be understood in terms of hydrogen abstraction from the solvent by perfluoro-n-propyllithium, while hexafluoropropene could form by the reactions,... 

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